Aromatic polyester textile fibers dyed with naphthyloxyanthraquinone dyes

ABSTRACT

New anthraquinone dyes, 1-amino-2-naphthyloxyalkoxy-4hydroxyanthraquinones, are provided. Synthetic textile fibers, in particular, polyethylene terephthalate fibers, when dyed with the new dyes, are colored in bright pink shades which are substantive, light fast, and sublimation resistant.

United States Patent [191 Genta [451 den. 22, 1974 1 AROMATIC POLYESTERTEXTILE FIBERS DYED WITH NAPHTHYLOXYANTHRAQUINONE DYES [75] Inventor:Guido R. Genta, Lock Haven, Pa.

[73] Assignee: American Aniline Products, Inc., Patterson, NJ.

[22] 7 Filed: Jan. 4, 1973 [21] Appl. No.: 320,845

Related US. Application Data [62] Division of Ser. No. 75,705, Sept. 25,1970.

521 user. 8/39 511 lnt.Cl D06p 3/52 {58] Field of Search 8/39 0, 39 R,179; 260/380 [56] References Cited FOREIGN PATENTS OR APPLICATIONS835,819 5/1960 Great Britain 7/1970 Great Britain 7/1965 Germany PrimaryExaminerDonald Levy Assistant Examiner-Bruce I-I. Hess Attorney, Agent,or Firr nJames E. Armstrong, III et [5 7] ABSTRACT 3 Claims, No DrawingsAROMATIC POLYESTER TEXTILE FIBERS DYED WITH NAPI-ITI-IYLOXYANTHRAQUINONEDYES This is a division of application Ser. No. 75,705, filed Sept. 25,1970.

BACKGROUND OF THE INVENTION Aromatic polyester fibers, such aspolyethylene terephthalate fibers, do not readily accept the highermolecular weight dyes, which generally provide dyeings of superiorphysical properties. As a result, it is difficult to find dyes ofacceptable shade and brightness which, when dyed by conventional methodson for example, polyethylene terephthalate, are acceptable in all of theimportant physical properties of substantivity, light fastness andresistance to sublimation. The standard of performance required withrespect to these physical properties has become increasingly criticalbecause of the demands of the textile industry. Recent standards aresuch that dyes which were considered acceptable or marginally acceptableseveral years ago are now regarded as unsuitable and have been replacedin the market by dyes of better overall performance.

I have discovered new anthraquinone dyes which give outstanding overallperformance when dyed on aromatic polyester fibers, particularly onpolyethylene terephthalate. The affinity for the fiber, light fastnessand resistance to sublimation of my new compounds is, by currentstandards, quite remarkable when considered in the light of theperformance of certain structurally similar materials. For example,Lodge, in US. Pat. No. 2,992,240, describes the use on polyester fibersof a series of 1-amino-4-hydroxy-2-substituted anthraquinones in whichthe 2-substituent is a lower alkoxy lower alkoxy or a monocyclic aryloxylower alkoxy radical. Typical dyes of this series, such asl-amino-Z-phenoxyethoxy-4-hydroxy anthraquinone, have acceptable shadeand good affinity for polyester fibers. However, such dyes have onlyfair sublimation characteristics, particularly at higher temperatures.Formerly, for fibers colored by either disperse dyeing or by theThermosol process, sublimation was evaluated at temperatures of 350 and400 F. A color which had good sublimation at temperatures up to 400F wasconsidered commercially desirable. Recently, colors are criticallyevaluated in the higher temperature ranges of 400 to 425 F and thedesired performance is good to excellent at such temperatures. My newdyes satisfy these modern commercial standard.

SUMMARY In accordance with the invention, I have discovered newanthraquinone dyes of the formula:

(I? NHz provide colored fibers of bright pink shades having outstandinglight and sublimation characteristics as well as good substantivity.

DETAILED DESCRIPTION The new dyes are made from l-amino-4-hydroxyanthraquinone compounds containing a halo, sulfo or phenoxy groupin the 2-position.

The anthraquinone compound is reacted with an alkali metal salt of aderivative of ethyl or propyl alcohol. The ethyl alcohol intermediate isconveniently made by the addition of one mole of ethylene oxide orethylenechlorohydrin to a naphthol which is either unsubstituted orappropriately substituted with chloro, bromo, lower alkyl, lower alkoxyor hydroxy groups. The pro pyl alcohol intermediates are made by theaddition of a mole of propylene oxide to the appropriate naphthol.Alternatively, the propyl alcohol intermediate can be prepared by thereaction of the appropriate hydroxy compound and epichlorohydrin,followed by hydrolysis. Another preparative method is to reactchloroacetone and a hydroxy compound, followed by reduction of thecarboxyl group to hydroxy]. Typical ethyl and propyl alcoholintermediates are those of the formula:

in which R is hydrogen or methyl and R is Z-naphthyl, l-naphthyl,4-chlorol-naphthyl, 2,4-dichlorol naphthyl, 2,4-dibromol -naphthyl, 5-chloro-2- naphthyl, S-bromo-Z-naphthyl, 4-methyl-1-naphthyl, 4-ethyll-naphthyl, 4-t-butyl-2-naphthyl, 6-methyll naphthyl,4,6-dimethyl-l-naphthyl, S-hydroxy-lnaphthyl, 6-hydroxyl -naphthyl,7-hydroxyl naphthyl, 7-hydroxy-2-naphthyl,5-hydroxy-2-naphthyl,5-,ethoxy-2-brorno-l-naphthyl, and 8-hydroxy-2- naphthyl.

Conveniently, the reaction is accomplished by mixing the anthraquinonecompound with a substantial excess of the alcohol intermediate, which isconverted to its alkali metal salt before reaction takes place. This isdone by heating the alcohol in the presence of sodium or potassiumhydroxide or carbonate in an amount sufficient to convert the hydroxylower alkyl group to the sodium or potassium salt thereof. The mixtureof anthraquinone compound and alcohol is heated to a temperature of atleast C, preferably to C, and held at that temperature until reaction iscomplete, which generally requires about 6 to 20 hours.

After the reaction is complete, an alcoholic solution of a mineral acidor organic acid, such as glacial acetic acid, previously diluted, isadded drop-wise to the mass. The product dye is recovered by filtrationand is washed first with denatured ethanol and subsequently with hotwater until it is free of acid, inorganic materials, and excess solvent.

The dye may be standardized either as a disperse paste or a dispersepowder by any of the basic standardizing techniques that have been knownto the art for many years, i.e., by the use of appropriate amounts ofcommon dispersants and standardizing agents, usually together with smallamounts of anionic wetting agent to assist in dispersion.

Standardized pastes are made by wet milling the dye in conventionalequipment in the presence of a dispersing agent, preferably sodiumlignin sulfonate or sodium alkylnaphthalene sulfonate. Various othercommercially available dispersing agents, such as sodium salts ofcarboxylated polyelectrolytes and the naphthalene sulfonates; e.g., thecondensation products of sulfonated naphthalene and formaldehyde, suchas sodium dinaphthylmethane disulfonate, are conveniently used. Thedispersed paste may be cut or standardized to a standard strength withwater. As noted above, any conventional wetting agent, e.g., sodiumcetyl sulfonate, may be added to wet out the product. The final colorcontent of the finished paste averages from -40 percent by weight (purecolor) active dye base.

Standardized dispersed powders are prepared by wet milling color in thepresence of a dispersant, such as those mentioned hereabove, inequipment, such as a ball mill, Werner-Pfleiderer mill or attritor. Thisdispersed material is oven or spray dried and micropulverized ifnecessary to provide the dispersed powder. The color is cut orstandardized to a standard strength in a blender with a diluent, such assodium sulfate or dextrin. A wetting agent, such as sodium cetyl sulfateor an alkylphenoxypolyethanol may be added to wet out the product.Dispersed powders are usually cut or standardized to 25-60 percent byweight color content (pure color).

The dye, when added to water with or without auxiliary agents, forms anear colloidal aqueous dispersion from which the aromatic polyesterfiber or textile material is dyed in the conventional manner at 40-l0OC(l042l2F) to give a colored fiber containing about 0.01-2 percent byweight dye (100% color basis).

Alternatively, dyeing may be accomplished without a carrier attemperatures of lOOl50C under pressure. Also, the dye may be applied inpatterns by conventional printing methods, if desired.

The dye can also be applied to the aromatic polyester fiber bythermofixation methods, such as the Thermosol" process. This process,which involves padding the cloth with the diluted dye dispersionfollowed by drying and heating the dried goods with hot air or heatedcontact rolls, is conveniently used for dyeing polyester fibers andblends containing these fibers. Temperatures of 180220C (ea. 360425F)are used for 30 to 90 seconds. If the fabric contains cotton or viscoserayon, apart from synthetic fibers, there is no danger of damagingcellulosic portions, but if wool is present, the temperature must bekept within l80-200C and the time must be reduced to 30 seconds.

In order to evaluate the effectiveness of a particular dye for a giventype of fiber, the dyed fiber is examined for substantivity of thecolor, light fastness of the color, and resistance of the color tosublimation. Specific tests for the evaluation of these importantproperties are described in the examples that follow.

My invention is further illustrated by the following examples:

EXAMPLE 1 To a one liter flask were charged 150 g. 2-(2-naphthyloxy)ethanol, 60 g. tetrahydrothiophene-l,ldioxide, and g.potassium carbonate, ground. The mixture was heated to 80-85C and 50 g.l-amino-2- phenoxy-4-hydroxyanthraquinone were added. The mixture wasthen heated to 145-l50C and was held at this temperature during 8 hours.After cooling to C, the mass was diluted with 320 g. denatured ethanolcontaining 15 g. glacial acetic acid. The diluted product was stirred anadditional 4 hours at 4045C, after which it was filtered, and washedwith 150 g. denatured ethanol and finally with hot water.

There was thus obtained 94 g. of 52% cake (49 g. pure dye) of a dye ofthe formula:

ll 0 i OH 4 A4 M i EXAMPLE 2 An aqueous dye bath containing 10% MarcronL (a commercially available phenolic dye carrier) and 1% monosodiumphosphate as a buffering agent was prepared. Type 54 Dacron polyesterfabric wa s tr eated in the bath at l 20 l for l0 minutes, the fabric towater dye bath ratio being 1:40. The disperse dye of Example 1 was addedin an amount sufficient to provide a bath containing a 2% dye based onthe weight of the polyester fiber. Dyeing was continued for one hour at205F and the fabric was removed from the bath, rinsed and dried.

Sample dyeings were tested for sublimation according to standard AATCCColor Fastness to Dry Heat (sublimation) Test No. l 17-1967T, Page B-74of the 1967 Technical Manual of the American Association of TextileChemists and Colorists. The dyed fabric was placed between a sandwich ofundyed Dacron polyester fabric swatches in an Atlas Scorch tester andheat was applied for 30 seconds. Sublimation tests were made at 350F,375F, 400F and 425F on goods dyed as described above. The new dye wascharacterized by nearly perfect sublimation at temperatures of 375F andbelow and very good to excellent sublimation at the temperatures of 400Fand 425F.

Similar excellent results were obtained when the dye was applied to thefabric by the Thermosol process and then tested for sublimation.

The dyeings were also tested for light fastness by subjecting them tocarbon are fading in accordance with AATCC Color Fastness to Light:Carbon Arc Lamp, Continuous Llght Test No. 16A-l964. The dyeings showedonly a very slight break at 100 hours exposure indicating superiorfastness to light.

EXAMPLE 3 The procedure of Example 1 was repeated with the exceptionthat g. of 2-( l-naphthyloxy )ethanol was used instead of the Z-naphthylderivative. The resulting product had the formula:

OCIhCIlz-O and was dispersed as described in Example 1. When tested forsublimation and light as described in Example 2, the sublimationcharacteristics were excellent and the light fastness substantiallyperfect up to 100 hours exposure.

EXAMPLE 4 For comparative purposes, the procedure of Example 1 wasfollowed with the exception that B-phenoxyethanol, 150 g., was used inplace of the 2-naphthyl derivative. The resulting product, correspondingto that of Example 2 of Lodge, US. Pat. No. 2,992,240, dyed Dacron in abright red shade having good substantivity and excellent light fastness.However, the sublimation characteristics at 400425F were only good tofair; thus significantly inferior when contrasted with the resultsobtained using the dyes of the present invention.

EXAMPLE 5-27 By repeating the procedure of Example 1, replacing the2-(2-naphthyloxy)ethanol with an equivalent amount of each of theintermediates shown in Table l, the resulting dyes give bright pinkshades with excellent sublimation and light fastness properties.

Example Intermediate Color of Number Dyed Polyester 5 2-[l-(4-chloronaphthyloxy)]ethanol bright pink 6 2-[l-(2,4-dichloronaphthyloxy)]ethanol 7 2-[ l 2,4-dibron1onaphthyloxy]ethanol 8 2-[ 2-( 5-chloronaphthyloxy lethanol 9 2-[ 2-(S-bromonaphthyloxy) ]ethanol l 2-[ l-( 4-methylnaphthyloxy ]ethanol l l2-[ l-(4-ethylnaphthyloxy)]ethanol l2 2-[ l( 4-5-butylnaphthyloxylethanol l3 2-[2-(4-methylnaphthyloxy)]ethanol l42-[2-(4-t-butylnaphthyloxy)]ethanol l5 2-[l-(6-methylnaphthyloxy)]ethanol l6 2-[ l-(4,G-dirnethylnaphthyloxy)]ethanol l7 2-[ l-(S-hydroxynaphthyloxy)Iethanol l8 2-[ l-( 6-hydroxynaphthyloxy lethanol l9 2-[ l-(7-hydroxynaphthyloxy) lethanol 20 2-[ 2-( Thydroxynaphthyloxy lethanol21 2-[ 2-( S-hydroxynaphthyloxy) lethanol 22 2-[ l2-bromo-S-methoxynaphthyloxy) ]ethanol 6 23 2-[ 2-( 8-hydroxynaphthyloxy]ethanol 24 2-( 2-naphthyloxy )propanol 25 2-( 1-naphthyloxy)propanol 262[ 2( S-bromonaphthyloxy ]propanol 27 2[2(-4-t-butylnaphthyloxy)]propanol The above dyes can also be used to dyecellulose acetate, cellulose triacetate and polyamide fibers in brightpink shades of good fastness properties.

I claim:

I. Aromatic polyester textile fibers dyed with a compound of the formulaII I [ I I I0 CH1CH;-O-i

| O O H 3. The aromatic polyester fibers of claim 1, wherein saidcompound is of the formula 2* w (m-ocmcm-o-[ij

2. The aromatic polyester fibers of claim 1, wherein said compound is ofthe formula
 3. The aromatic polyester fibers of claim 1, wherein saidcompound is of the formula